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WO1995005356A1 - Procede pour produire de l'anhydride acetique seul ou en combinaison avec de l'acide acetique - Google Patents

Procede pour produire de l'anhydride acetique seul ou en combinaison avec de l'acide acetique Download PDF

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Publication number
WO1995005356A1
WO1995005356A1 PCT/JP1994/001354 JP9401354W WO9505356A1 WO 1995005356 A1 WO1995005356 A1 WO 1995005356A1 JP 9401354 W JP9401354 W JP 9401354W WO 9505356 A1 WO9505356 A1 WO 9505356A1
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WO
WIPO (PCT)
Prior art keywords
acetate
acetic anhydride
reactor
product
methyl
Prior art date
Application number
PCT/JP1994/001354
Other languages
English (en)
Japanese (ja)
Inventor
Yoshiaki Morimoto
Hiroto Tanigawa
Kazuyuki Akita
Original Assignee
Daicel Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=16481515&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1995005356(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Daicel Chemical Industries, Ltd. filed Critical Daicel Chemical Industries, Ltd.
Priority to DE69414361T priority Critical patent/DE69414361T3/de
Priority to JP50340695A priority patent/JP3500150B2/ja
Priority to EP94922379A priority patent/EP0665210B2/fr
Priority to KR1019950701381A priority patent/KR0168207B1/ko
Priority to US08/406,896 priority patent/US5648531A/en
Publication of WO1995005356A1 publication Critical patent/WO1995005356A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/573—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/12—Acetic anhydride

Definitions

  • the present invention relates to a method for producing acetic anhydride or acetic anhydride and acetic acid.
  • the present invention relates to a method for producing acetic anhydride or acetic anhydride and acetic acid by reacting with carbon and hydrogen.
  • Acetic acid is a basic compound necessary for many industries, including the polymer and chemical industries, which are used in large quantities as raw materials for acetates, acetic anhydride, vinyl acetate, and terephthalic acid.
  • Acetic anhydride is a compound that is used in large quantities as a raw material for producing cellulose acetate and is also useful as a raw material for chemicals such as pharmaceuticals, fragrances and dyes.
  • Acetic acid and acetic anhydride are interrelated chemical substances for practical use. For example, in the cellulose acetate industry, acetic anhydride is produced from acetic acid, acetic anhydride is reacted with cellulose, and cellulose acetate and acetic acid are reused.
  • acetic anhydride was produced from ketene obtained by thermally decomposing acetic acid. Recently, however, a method has been developed for producing acetic anhydride from methyl acetate or dimethyl ether and carbon monoxide. This reaction is a catalytic reaction using a rhodium compound and methyl iodide as main catalysts, but the reaction speed is slow only with the main catalyst, and various cocatalysts have been proposed.
  • the function required of the cocatalyst is to promote the reaction between methyl acetate or dimethyl ether and carbon monoxide to the extent industrially feasible. However, it is desirable that the addition of the smallest possible amount has a large accelerating effect and that the amount of by-products and tar generated is small.
  • US Pat. No. 4,364,907 discloses a method in which tar extracted with an HI aqueous solution is further extracted with aqueous ammonia to recover an additional amount of rhodium from the tar.
  • this method requires the use of ammonia and the removal of this ammonia from the process stream which must be returned to the subsequent reaction.
  • Various other methods have been tried (US Pat. No. 4,476,238), but at present no method has been found to easily and effectively remove tar.
  • the presence of tar reduces the catalytic activity, and the inclusion of iodine and precious metal catalysts
  • the carbonylation reaction is terminated by inactivating the catalyst, and it is therefore desired that the catalyst is not present in the reaction system as much as possible in a tar state.
  • FIG. 1 is an example of a flow chart of a method for producing acetic acid and acetic anhydride in the present invention.
  • 1 is a reactor
  • 2 is an evaporation tank
  • 3 is a first distillation column
  • 4 is a second distillation column
  • 5 is a third distillation column. Disclosure of the present invention
  • the present invention uses a rhodium compound and methyl iodide as main catalysts, and continuously reacts dimethyl ether and / or methyl acetate, and optionally water and / or methanol with carbon monoxide or carbon monoxide and hydrogen.
  • Acetic anhydride or a method for producing acetic anhydride and acetic acid The method is characterized in that a trace amount of pure substance causing tar generation is separated in an evaporating tank and a purification step, and the trace impurity is removed.
  • the present invention relates to acetic anhydride or a method for producing acetic anhydride and acetic acid.
  • the present invention provides the following. Using a rhodium compound and methyl iodide as the main catalyst, continuously reacting dimethyl ether and / or methyl acetate, and optionally water and / or methanol with carbon monoxide or carbon monoxide and hydrogen, The reaction solution is introduced into an evaporating tank having a lower pressure than the reactor, and a volatile phase containing the product, unreacted dimethyl ether and / or methyl acetate and methyl iodide, and a non-volatile containing the above-mentioned dimethyl compound And the volatile phase is distilled to obtain a product and a distillate containing unreacted dimethyl ether and z or methyl acetate and methyl iodide, and the distillate is fed to a carbonylation reactor.
  • tar aldehyde and z or vinyl acetate by-produced in the reactor or in the subsequent evaporating tank are separated and removed in the evaporating tank and in the z or subsequent purification step, whereby tar is removed.
  • the amount of by-products is minimized by decomposing ethylidene diacetate, which is a by-product in the reactor or the subsequent evaporating tank, by adding water to the catalyst solution recycled from the evaporating tank to the reactor. .
  • methyl acetate, dimethyl ether and methanol are preferable.
  • the amount of methanol used as a raw material for the reaction is closely related to the production amount of acetic acid, and thus may not be used if necessary.
  • Methyl acetate and dimethyl ether can be used simultaneously. Also, if necessary May be used.
  • Carbon monoxide is used as another raw material in the reactor, but a small amount of hydrogen gas can be charged to the reactor as already known (US Pat. No. 4,374,070).
  • the amount of hydrogen gas charged is such that the hydrogen partial pressure inside the reactor becomes 0.5 atm or more.
  • the hydrogen partial pressure is preferably within 5 atm.
  • the partial pressure of carbon monoxide is set in the range of 10 to 100 atm.
  • the rhodium compound which is one of the main catalysts in the reaction, may be of any form as long as it can be dissolved in the reaction solution under the reaction conditions, for example, halide salts, nitrates, sulfates, etc.
  • An inorganic salt, an organic acid salt such as a carboxylate, a carbon monoxide, an organic rhodium complex coordinated with phosphine, or the like can be used.
  • the rhodium concentration is preferably from 100 to 3, OO O pm.
  • Methyl iodide another main catalyst of the first force-ponylation reaction, can be used in the reaction solution in a concentration range of 5 to 30 wt%, and the reaction is carried out in the range of 150 to 250, and the reaction pressure is Is carried out in the range of 10 to 100 atmospheres, preferably 20 to 50 atmospheres.
  • reaction solvent acetic anhydride and / or acetic acid is preferably used, but other organic solvents can also be used.
  • the reaction can be carried out in any of a batch reaction mode and a continuous reaction mode, but from a more practical viewpoint, it is preferable to carry out the reaction in a continuous reaction mode.
  • the process will be described with reference to FIG.
  • the raw material, the catalyst, and the solvent are continuously introduced into the high-temperature high-pressure reactor (1).
  • the reaction solution in the reactor is continuously withdrawn, and the product is separated, so the evaporating tank (2) with lower pressure than the reactor Will be introduced.
  • the product may be extracted in a vapor state or may be extracted as a reaction solution.
  • acetic anhydride as a product
  • methyl iodide as a catalyst
  • unreacted methyl acetate and dimethyl ether acetic acid as a solvent
  • minute amounts of by-products are produced.
  • Acetaldehyde and vinyl acetate are evaporated and sent to the purification process.
  • a liquid containing a mouth dime compound which is a main catalyst, is withdrawn from the bottom of the evaporator tank and is circulated to the reactor.
  • the evaporation tank may be a flash evaporation type or a distillation column type having several stages (one or more stages).
  • the evaporation tank is a distillation column type.
  • a distillation column As the evaporating tank, the content of acetoaldehyde and z or vinyl acetate in the liquid circulated from the bottom of the evaporating tank to the reactor can be further reduced, and tar production can be reduced.
  • impurities are separated and removed by distillation using a distillation column type evaporation tank instead of flash evaporation.
  • the liquid components that did not evaporate in the evaporating tank are returned to the reactor, including rhodium and cocatalyst.
  • a small amount of ethylidene diacetate, which causes tar generation, is concentrated in this liquid, but this ethylidene diacetate is easily decomposed by water.
  • Decomposition by water changes to vinyl acetate, a very low boiling point trace component, but vinyl acetate easily evaporates and separates in the evaporation tank. Therefore, an appropriate amount of water may be added to the liquid components that did not evaporate in the evaporator, but adding water to the liquid that did not evaporate in the evaporator changes the production ratio of acetic acid and acetic anhydride.
  • adjustment of the production balance of acetic acid and acetic anhydride is This is done with methanol and methyl acetate and Z or dimethyl ether and / or water charged to the reactor.
  • methanol and methyl acetate and Z or dimethyl ether and / or water charged to the reactor As a method of adding water to the liquid that has not evaporated in the evaporating tank, only water may be directly charged into the evaporating tank bottom pipe, or a hydrolysis reactor may be provided.
  • the water decomposition temperature is preferably from 10 to 300 ° C.
  • relatively low-boiling components such as methyl iodide, methyl acetate, dimethyl ether, etc. are separated from the components evaporated from the evaporating tank, returned to the reactor, and recycled. used.
  • the distillate from the distillation column composed of relatively low-boiling components contains acetaldehyde and Z or vinyl acetate which cause tar generation when circulated to the reactor. Therefore, it is preferable to remove vinyl acetate from the first distillation column as much as possible by providing a sufficient number of stages and / or reflux ratio of the first distillation column.
  • vinyl acetate When vinyl acetate is discharged from the first distillation column, it must be separated and removed from the product acetic acid and acetic anhydride in the second distillation column.
  • specific methods for separating vinyl acetate, product acetic acid, and acetic anhydride include the following methods. That is, in the second distillation column, low-boiling components that cause tar generation are distilled off from the top of the column, and acetic acid is separated by a side cut from below the distillation column preparation stage. Further, acetic anhydride is removed from the bottom of the distillation column.
  • a mixture of acetic acid and acetic anhydride may be extracted from the second distillation column, and separated and purified into product acetic acid and product acetic anhydride in a new distillation column.
  • methyl iodide, methyl acetate A small amount of acetate aldehyde contained in the liquid consisting of methyl ether is distilled off in the third distillation column (5), and methyl iodide, methyl acetate and dimethyl ether are removed from the third distillation column and reacted in the reactor. Circulate and reuse. Either one of these separation and removal of acetate aldehyde and the separation and removal of vinyl acetate by distillation may be used alone, or both may be combined.
  • the liquid was directly circulated from the first distillation column to the reactor, and was a liquid containing a large amount of vinyl acetate and acetoaldehyde.However, acetoaldehyde was separated by distillation in the third distillation column. As a result, the production amount of tar can be reduced.
  • the method or the method of distilling and removing acetate in the third distillation column (5) may be used alone, but it is more preferable to use them in combination.
  • Example 1 The procedure was performed in the same manner as in Example 1-, except that the evaporating fraction from the evaporating tank was fed into the first distillation column having 60 actual stages and separated at a reflux ratio of 3. In this case, the separation ability of vinyl acetate in the first distillation column was improved, and the amount of vinyl acetate circulating in the reaction system was reduced to 16% of Example 1.
  • the by-product rate of tar was 0.0004 g (tar) / 100 g (product acetic acid + product acetic anhydride).
  • Example 1 The same procedure was performed as in Example 1 except that the reflux ratio of the first distillation column was set to 5. ⁇ In this case, the ability of the first distillation column to separate vinyl acetate was improved, and the amount of vinyl acetate circulating in the reaction system was increased. Was reduced to 42% of Example 1.
  • the by-product rate of tar was O. OO lg (tar) / 100 g (product acetic acid + product acetic anhydride) o
  • the boil-off of the first distillation column was slightly dropped, that is, the amount of methyl acetate withdrawn from the bottom of the first distillation column was increased to 10 times that of Example 1, and the distillate of the first distillation column was removed. Feed to the third distillation column, the top of the third distillation column
  • the procedure was performed in the same manner as in Example 1 except that acetyl aldehyde was distilled off from Example 1.
  • Acetic acid and acetic anhydride were removed in the first distillation column and separated and commercialized in the second distillation column. In this case, the amount of vinyl acetate circulating in the reaction system was reduced to .4.8% in Example 1.
  • the by-product rate of tar was 0.0001 g (tar) / 100 g (product acetic acid + product acetic anhydride).
  • Example 6 The procedure was performed in the same manner as in Example 1 except that the evaporation tank was a 15-stage distillation column and the reflux ratio of the evaporation tank was 1. In this case, the amount of vinyl acetate circulating in the reaction system was reduced to 10% of Example 1.
  • the by-product rate of tar was 0.0002 g (tar) Z 100 g (product acetic acid + product acetic anhydride), Example 6

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Est décrit un procédé pour produire de l'anhydride acétique seul ou en combinaison avec de l'acide acétique par réaction d'acétate de méthyle et/ou d'éther diméthylique et, comme constituant(s), optionnel(s), d'eau et/ou de méthanol avec du monoxyde de carbone seul ou en combinaison avec de l'hydrogène en présence d'un composé de rhodium et d'iodure méthylique comme principaux catalyseurs. Dans ce procédé, les impuretés à l'état de trace à l'origine de la production de goudron sont éliminées par séparation de celles-ci par distillation dans l'évaporateur et/ou dans l'étape de raffinage ultérieure, ce qui permet de réduire la production du goudron qui sinon se transforme en contaminant.
PCT/JP1994/001354 1993-08-18 1994-08-16 Procede pour produire de l'anhydride acetique seul ou en combinaison avec de l'acide acetique WO1995005356A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE69414361T DE69414361T3 (de) 1993-08-18 1994-08-16 Verfahren zur herstellung von acetanhydrid oder einer mischung von acetanhydrid und essigsäure
JP50340695A JP3500150B2 (ja) 1993-08-18 1994-08-16 無水酢酸又は無水酢酸及び酢酸の製造方法
EP94922379A EP0665210B2 (fr) 1993-08-18 1994-08-16 Procede pour produire de l'anhydride acetique seul ou en combinaison avec de l'acide acetique
KR1019950701381A KR0168207B1 (ko) 1993-08-18 1994-08-16 무수아세트산 또는 무수아세트산 및 아세트산의 제조방법
US08/406,896 US5648531A (en) 1993-08-18 1994-08-16 Process for producing acetic anhydride alone or acetic anhydride and acetic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5/203896 1993-08-18
JP20389693 1993-08-18

Publications (1)

Publication Number Publication Date
WO1995005356A1 true WO1995005356A1 (fr) 1995-02-23

Family

ID=16481515

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1994/001354 WO1995005356A1 (fr) 1993-08-18 1994-08-16 Procede pour produire de l'anhydride acetique seul ou en combinaison avec de l'acide acetique

Country Status (8)

Country Link
US (1) US5648531A (fr)
EP (1) EP0665210B2 (fr)
JP (1) JP3500150B2 (fr)
KR (1) KR0168207B1 (fr)
CN (1) CN1040101C (fr)
DE (1) DE69414361T3 (fr)
TW (1) TW339329B (fr)
WO (1) WO1995005356A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002512995A (ja) * 1998-04-24 2002-05-08 イーストマン ケミカル カンパニー 無水酢酸の製造方法
WO2007040087A1 (fr) * 2005-10-03 2007-04-12 Daicel Chemical Industries, Ltd. Procédé de production d'acide acétique
JP4994549B2 (ja) * 1999-08-31 2012-08-08 セラニーズ・インターナショナル・コーポレーション 改良された不純物特性をもつメタノールカルボニル化法のためのロジウム／無機ヨウ化物触媒系
US8967361B2 (en) 2013-02-27 2015-03-03 Outerwall Inc. Coin counting and sorting machines
US9022841B2 (en) 2013-05-08 2015-05-05 Outerwall Inc. Coin counting and/or sorting machines and associated systems and methods
US9036890B2 (en) 2012-06-05 2015-05-19 Outerwall Inc. Optical coin discrimination systems and methods for use with consumer-operated kiosks and the like
US9443367B2 (en) 2014-01-17 2016-09-13 Outerwall Inc. Digital image coin discrimination for use with consumer-operated kiosks and the like

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CN1198781C (zh) * 1995-04-27 2005-04-27 大赛璐化学工业株式会社 制备醋酸的方法
IN192600B (fr) * 1996-10-18 2004-05-08 Hoechst Celanese Corp
US7271293B2 (en) * 2004-03-02 2007-09-18 Celanese International Corporation Control method for process of removing permanganate reducing compounds from methanol carbonylation process
CN100417445C (zh) * 2005-12-05 2008-09-10 上海焦化有限公司 一种制备醋酐的催化组合物及其应用
US7737298B2 (en) * 2006-06-09 2010-06-15 Eastman Chemical Company Production of acetic acid and mixtures of acetic acid and acetic anhydride
US9012683B2 (en) 2010-11-12 2015-04-21 Eastman Chemical Company Coproduction of acetic acid and acetic anhydride
CN102381956B (zh) * 2011-09-06 2013-08-21 安徽皖维高新材料股份有限公司 醋酸甲酯和甲醇共沸物羰基合成醋酐、醋酸及分离方法
CN102430247B (zh) * 2011-09-06 2014-09-03 安徽皖维高新材料股份有限公司 一种羰基合成醋酐中分离系统焦油的处理方法
TWI500820B (zh) * 2012-03-05 2015-09-21 製造高純度一氧化碳之設備
US8759576B2 (en) 2012-09-06 2014-06-24 Celanese International Corporation Processes for purifying acetic anhydride
CN103450002A (zh) * 2013-07-26 2013-12-18 常州大学 一种对称酸酐的合成方法
US9908835B2 (en) 2015-11-13 2018-03-06 Celanese International Corporation Processes for purifying acetic and hydrating anhydride

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EP0497521A2 (fr) * 1991-01-28 1992-08-05 Hoechst Celanese Corporation Elimination de la contamination carbonylée à partir du courant du procédé de carbonylation

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002512995A (ja) * 1998-04-24 2002-05-08 イーストマン ケミカル カンパニー 無水酢酸の製造方法
JP4994549B2 (ja) * 1999-08-31 2012-08-08 セラニーズ・インターナショナル・コーポレーション 改良された不純物特性をもつメタノールカルボニル化法のためのロジウム／無機ヨウ化物触媒系
WO2007040087A1 (fr) * 2005-10-03 2007-04-12 Daicel Chemical Industries, Ltd. Procédé de production d'acide acétique
US9036890B2 (en) 2012-06-05 2015-05-19 Outerwall Inc. Optical coin discrimination systems and methods for use with consumer-operated kiosks and the like
US9594982B2 (en) 2012-06-05 2017-03-14 Coinstar, Llc Optical coin discrimination systems and methods for use with consumer-operated kiosks and the like
US8967361B2 (en) 2013-02-27 2015-03-03 Outerwall Inc. Coin counting and sorting machines
US9022841B2 (en) 2013-05-08 2015-05-05 Outerwall Inc. Coin counting and/or sorting machines and associated systems and methods
US9443367B2 (en) 2014-01-17 2016-09-13 Outerwall Inc. Digital image coin discrimination for use with consumer-operated kiosks and the like

Also Published As

Publication number Publication date
TW339329B (en) 1998-09-01
DE69414361T3 (de) 2006-06-29
KR950703505A (ko) 1995-09-20
CN1113655A (zh) 1995-12-20
EP0665210B2 (fr) 2005-11-23
KR0168207B1 (ko) 1999-03-20
CN1040101C (zh) 1998-10-07
EP0665210B1 (fr) 1998-11-04
EP0665210A4 (fr) 1996-01-17
DE69414361T2 (de) 1999-04-01
US5648531A (en) 1997-07-15
JP3500150B2 (ja) 2004-02-23
EP0665210A1 (fr) 1995-08-02
DE69414361D1 (de) 1998-12-10

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